CN102690378B - Modified propylene polymer - Google Patents

Abstract

The invention discloses the modified propylene polymer of excellence aspect a kind of balance between melt tension and mobility, described modified propylene polymer can be by by the obtaining containing the reaction of the compound (B) of ethylenic unsaturated bond and the organic peroxide (C) of 0.01-20 weight portion of the acrylic polymers of 100 weight portions (A), 0.1-50 weight portion, wherein under the load of 2.16Kg in 230 DEG C of melt flow rate (MFR)s that record and the formula (1) below 190 DEG C of melt tensions that record meet: MT > 9 × MFR^(-0.9)…(1)。

Description

Modified Propylene Polymer

technical field

This invention relates to modified propylene polymers.

Background technique

It is known that modified polyolefin resins can be obtained by grafting polar monomers such as maleic anhydride, glycidyl methacrylate onto propylene polymers.

For example, Patent Document 1 discloses a modified propylene polymer which can be obtained by combining a functional compound having a carboxylic acid group with a compound having at least two or more functional groups reactive with carboxylic acid in the same molecule. and organic peroxides; then, they are subjected to a grafting reaction.

Patent Document 2 discloses a modified propylene polymer obtainable by melt-mixing a mixture of a propylene-containing polymer, a metal salt of (meth)acrylic acid, and an organic peroxide; stick reaction.

Related literature

patent documents

[Patent Document 1]: JP2003-171515A

[Patent Document 2]: JP2009-179666A

In the grafting reaction, due to the use of the organic peroxide, the cleavage of the molecular chain of the propylene polymer and the grafting reaction occur simultaneously. Therefore, the molecular weight of the modified propylene polymer obtained after the grafting reaction becomes significantly lower than that of the propylene polymer before modification, resulting in a marked increase in fluidity and a marked decrease in melt tension. For this reason, modified propylene polymers have problems in that their moldability is inferior to that of propylene polymers and no longer retain the inherent mechanical properties of propylene polymers.

The modified propylene polymer disclosed in Patent Document 1 has a high melt tension, but the modified propylene polymer cannot be alloyed with a different type because its carboxylic acid as a polar component has been mixed with other polymer compounds The reaction is exhausted.

Moreover, although the grafted amount of the modified propylene polymer disclosed in Patent Document 2 is increased, the high fluidity of the modified propylene polymer is not disclosed, and the disclosed polymer has a balance between fluidity and melt tension. The balance aspect is not necessarily satisfactory.

In view of the problems described above, an object of the present invention is to provide a modified propylene polymer excellent in the balance between melt tension and fluidity.

Contents of the invention

The invention provides a modified propylene polymer, which is obtained by reacting the following components: 100 parts by weight of propylene polymer (A); based on the 100 parts by weight, 0.1-50 parts by weight of A compound (B) belonging to an unsaturated bond; based on the 100 parts by weight of the organic peroxide (C) of 0.01-20 parts by weight,

Wherein, the melt flow rate measured at 230°C under a load of 2.16Kg and the melt tension measured at 190°C satisfy the following formula (1):

MT＞9×MFR ^(-0.9) ......(1)

Among them, MT refers to melt tension and MFR refers to melt flow rate.

According to the present invention, it becomes possible to provide a modified propylene polymer excellent in the balance between melt tension and fluidity.

detailed description

Modified Propylene Polymer

The modified propylene polymer according to the present invention can be prepared by reacting the propylene polymer (A), the ethylenically unsaturated bond-containing compound (B) and the organic peroxide (C) together.

From the viewpoint of molding processability of the modified propylene polymer, the melt flow rate (MFR) of the modified propylene polymer measured at 230° C. (according to JIS K7210) under a load of 2.16 Kg is preferably 0.1 to 400 g/ 10 minutes, more preferably 0.5-300 g/10 minutes, still more preferably 1-200 g/10 minutes.

Also, the melt flow rate and melt tension (MT) of the modified propylene polymer satisfy the relationship represented by the following formula (1):

MT＞9×MFR ^(-0.9) ......(1)

If the relationship between the melt flow rate and the melt tension deviates from the above formula (1), the moldability of the modified propylene polymer will decrease. The relationship between melt flow rate and melt tension is preferably MT>10×MFR ^(-0.9) , more preferably MT>12×MFR ^(-0.9) .

The graft ratio of the ethylenically unsaturated bond-containing compound (B) to the propylene polymer (A), that is, the modification ratio, is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, or More preferably, it is 0.1 to 1% by weight.

The value determined using the infrared absorption spectrum of the modified propylene polymer is used as the modification rate in the present invention.

The relevant components will be described below.

<Propylene polymer (A)>

The propylene polymer (A) (hereinafter also referred to as component (A)) used in the present invention means a propylene homopolymer, or a copolymer of propylene and other monomers. These may be used alone, or alternatively two or more of them may be used in a blend. The aforementioned copolymers may be either random copolymers or block copolymers.

Examples of random copolymers include: random copolymers composed of structural units derived from propylene and structural units derived from ethylene; structures composed of structural units derived from propylene and structural units derived from other α-olefins other than propylene A random copolymer composed of units; a random copolymer composed of structural units derived from propylene, structural units derived from ethylene, and structural units derived from other α-olefins other than propylene.

Examples of block copolymers include: a polymer component consisting of a propylene homopolymer component or a structural unit derived from propylene (hereinafter referred to as polymer component (I)), and propylene with ethylene and/or α - A polymer material consisting of a copolymer component of olefins (hereinafter referred to as polymer component (II)).

The propylene polymer (A) has an ^isotactic pentad fraction (sometimes written as [ mmmm] fraction) is preferably 0.97 or higher, more preferably 0.98 or higher. Measurements indicate that the closer the isotactic pentad fraction of the propylene polymer (A) is to 1, the higher the tacticity of the molecular structure of the highly crystalline polymer, ie, the propylene resin (A).

When the propylene polymer (A) is a random copolymer similar to the above or a block copolymer similar to the above, the value measured for the propylene unit chain in the copolymer is used.

From the standpoint of the balance between the tensile strength and impact resistance of the resulting molded article and the molding processability of the resin composition, the melt of the propylene copolymer (A) measured at 230°C under a load of 2.16 Kg The flow rate (MFR) is preferably 0.05-500 g/10 min, more preferably 1-120 g/10 min, still more preferably 1-80 g/10 min, most preferably 5-50 g/10 min.

The propylene polymer (A) can be prepared by the method described below using conventional polymerization catalysts.

Examples of the polymerization catalyst include: Ziegler type catalyst systems; Ziegler-Natta type catalyst systems; catalysts consisting of alkylaluminoxanes and compounds of transition metals of Group 4 of the periodic table containing cyclopentadiene rings system; a catalyst system composed of an organoaluminum compound, a compound of a transition metal of Group 4 of the periodic table containing a cyclopentadiene ring, and a compound capable of reacting with a transition metal compound to form an ionic complex; A catalyst system obtained by modifying inorganic particles such as silicon dioxide and clay minerals supported by compounds of transition metals of Group 4 of the periodic table of pentadiene rings, compounds capable of forming ionic complexes, and organoaluminum compounds. Prepolymerized catalysts prepared by prepolymerizing ethylene or alpha-olefins in the presence of a catalyst system as described above may also be used.

Specific examples of the catalyst system include those disclosed in JP61-218606A, JP5-194685A, JP7-216017A, JP9-316147A, JP10-212319A and JP2004-182981A.

Examples of polymerization methods include bulk polymerization, solution polymerization, slurry polymerization and gas phase polymerization. Bulk polymerization refers to the method of polymerizing liquid olefins as a medium at the polymerization temperature, while solution polymerization or slurry polymerization is carried out in inert hydrocarbon solvents such as propane, butane, isobutane, pentane, hexane, heptane and octane method of polymerization in alkanes. The gas phase polymerization refers to a method in which a gaseous monomer is used as a medium and the gaseous monomer is polymerized in the medium.

These polymerization methods can be carried out either by a batch system or by a multistage system in which a plurality of polymerization reactors are connected in series, and these polymerization methods can be appropriately combined. From the viewpoint of industry and economy, a continuous gas phase polymerization method or a bulk gas phase polymerization method is preferable, wherein the bulk polymerization method and the gas phase polymerization method are used continuously.

The conditions of each polymerization step (polymerization temperature, polymerization pressure, monomer concentration, catalyst input amount, polymerization time, etc.) can be appropriately determined according to the desired propylene polymer (A).

In the preparation of the propylene polymer (A), in order to remove the residual solvent contained in the propylene polymer (A) or the ultra-low molecular weight oligomers produced during the preparation process, the propylene polymer (A) can be Drying is performed at a temperature at which the propylene polymer (A) melts. Examples of drying methods include those disclosed in JP55-75410A and JP2565753.

· Random copolymerization

As mentioned above, the random copolymer in the present invention includes: a random copolymer composed of a structural unit derived from propylene and a structural unit derived from ethylene; a random copolymer composed of a structural unit derived from propylene and a structural unit derived from Random copolymers composed of structural units of other α-olefins; random copolymers composed of structural units derived from propylene, structural units derived from ethylene, and structural units derived from other α-olefins other than propylene.

The α-olefin other than propylene constituting the random copolymer is preferably an α-olefin having 4 to 10 carbon atoms, examples of which include 1-butene, 1-pentene, 1-hexene, 4-methene 1-pentene, 1-octene and 1-decene, preferably 1-butene, 1-hexene or 1-octene.

Examples of random copolymers composed of structural units derived from propylene and structural units derived from α-olefins include: propylene-1-butene random copolymer, propylene-1-hexene random copolymer, propylene- 1-octene random copolymer and propylene-1-decene random copolymer.

Examples of random copolymers composed of structural units derived from propylene, structural units derived from ethylene, and structural units derived from α-olefins include: propylene-ethylene-1-butene random copolymer, propylene-ethylene- 1-hexene random copolymer, propylene-ethylene-1-octene random copolymer, and propylene-ethylene-1-decene random copolymer.

The content of the structural unit derived from ethylene and/or α-olefin in the random copolymer is preferably 0.1 to 40% by weight, more preferably 0.1 to 30% by weight, still more preferably 2 to 15% by weight. The content of the structural unit derived from propylene is preferably 99.9-60% by weight, more preferably 99.9-70% by weight, still more preferably 98-85% by weight.

·Block copolymer

As mentioned above, the block copolymer in the present invention refers to a polymer component composed of a propylene homopolymer component or a structural unit derived from propylene (hereinafter referred to as polymer component (I)) and propylene A polymer material composed of a copolymer component with ethylene and/or α-olefin (hereinafter referred to as polymer component (II)).

The polymer component (I) refers to a propylene homopolymer component or a polymer component composed of structural units derived from propylene. Examples of the polymer component composed of structural units derived from propylene include: units derived from at least one comonomer selected from ethylene and α-olefins having 4 to 10 carbon atoms and units derived from propylene Composed of propylene copolymer components.

When the polymer component (I) is composed of a polymer component derived from a structural unit of propylene, a structure derived from at least one comonomer selected from ethylene and α-olefins containing 4 to 10 carbon atoms The content of the unit is greater than or equal to 0.01% by weight and less than 20% by weight, wherein the polymer component

The weight of (I) is 100% by weight.

As the ?-olefin having 4 to 10 carbon atoms, 1-butene, 1-hexene and 1-octene are preferable, and 1-butene is more preferable.

Examples of polymer components composed of structural units derived from propylene include: propylene-ethylene copolymer components, propylene-1-butene copolymer components, propylene-1-hexene copolymer components, propylene-1 - an octene copolymer component, a propylene-ethylene-1-butene copolymer component, a propylene-ethylene-1-hexene copolymer component, and a propylene-ethylene-1-octene copolymer component.

Examples of the polymer component (I) preferably include: a propylene homopolymer component, a propylene-ethylene copolymer component, a propylene-1-butene copolymer component, and a propylene-ethylene-1-butene copolymer components.

The polymer component (II) means a copolymer component consisting of structural units derived from at least one comonomer selected from ethylene and α-olefins containing 4 to 10 carbon atoms and structural units derived from propylene .

The content of structural units derived from at least one comonomer selected from ethylene and α-olefins containing 4-10 carbon atoms contained in the polymer component (II) is 20-80% by weight, preferably 20% - 60% by weight, more preferably 30-60% by weight, wherein the weight of polymer component (II) is 100% by weight.

Examples of the α-olefins having 4 to 10 carbon atoms constituting the polymer component (II) include the same α-olefins as the α-olefins having 4 to 10 carbon atoms constituting the aforementioned polymer component (I) .

Examples of the polymer component (II) include: propylene-ethylene copolymer component, propylene-ethylene-1-butene copolymer component, propylene-ethylene-1-hexene copolymer component, propylene-ethylene-1 - Octene copolymer component, propylene-ethylene-1-decene copolymer component, propylene-1-butene copolymer component, propylene-1-hexene copolymer component, propylene-1-octene copolymer material components, and propylene-1-decene copolymer components; preferably propylene-ethylene copolymer components, propylene-1-butene copolymer components and propylene-ethylene-1-butene copolymer components, more Preference is given to propylene-ethylene copolymer components.

The content of the polymer component (II) in the polymer material composed of the polymer component (I) and the polymer component (II) is preferably 1-50% by weight, more preferably 1-40% by weight, still more Preferably it is 10-40% by weight, most preferably 10-30% by weight, wherein the weight of propylene polymer (A) is 100% by weight.

When the polymer component (I) in the propylene copolymer composed of the polymer component (I) and the polymer component (II) is a propylene homopolymer component, examples of the propylene copolymer include: (propylene)- (propylene-ethylene) copolymer, (propylene)-(propylene-ethylene-1-butene) copolymer, (propylene)-(propylene-ethylene-1-hexene) copolymer, (propylene)-(propylene-ethylene -1-octene) copolymer, (propylene)-(propylene-1-butene) copolymer, (propylene)-(propylene-1-hexene) copolymer, (propylene)-(propylene-1-octene ) copolymers, and (propylene)-(propylene-1-decene) copolymers.

When the polymer component (I) in the polymer material consisting of the polymer component (I) and the polymer component (II) is a propylene copolymer component composed of units derived from propylene, the polymer component Examples of propylene copolymers composed of component (I) and polymer component (II) include: (propylene-ethylene)-(propylene-ethylene) copolymer, (propylene-ethylene)-(propylene-ethylene-1-butene ) copolymer, (propylene-ethylene)-(propylene-ethylene-1-hexene) copolymer, (propylene-ethylene)-(propylene-ethylene-1-octene) copolymer, (propylene-ethylene)-(propylene - (ethylene-1-decene) copolymer, (propylene-ethylene)-(propylene-1-butene) copolymer, (propylene-ethylene)-(propylene-1-hexene) copolymer, (propylene-ethylene) -(propylene-1-octene) copolymer, (propylene-ethylene)-(propylene-1-decene) copolymer, (propylene-1-butene)-(propylene-ethylene) copolymer, (propylene-1 -butene)-(propylene-ethylene-1-butene) copolymer, (propylene-1-butene)-(propylene-ethylene-1-hexene) copolymer, (propylene-1-butene)-( Propylene-ethylene-1-octene) copolymer, (propylene-1-butene)-(propylene-ethylene-1-decene) copolymer, (propylene-1-butene)-(propylene-1-butene ) copolymer, (propylene-1-butene)-(propylene-1-hexene) copolymer, (propylene-1-butene)-(propylene-1-octene) copolymer, (propylene-1-butene ene)-(propylene-1-decene) copolymer, (propylene-1-hexene)-(propylene-1-hexene) copolymer, (propylene-1-hexene)-(propylene-1-octene ) copolymer, (propylene-1-hexene)-(propylene-1-decene) copolymer, (propylene-1-octene)-(propylene-1-octene) copolymer, and (propylene-1- octene)-(propylene-1-decene) copolymer.

Preferred examples of propylene copolymers consisting of polymer component (I) and polymer component (II) include: (propylene)-(propylene-ethylene) copolymer, (propylene)-(propylene-ethylene-1-butyl ethylene) copolymer, (propylene-ethylene)-(propylene-ethylene) copolymer, (propylene-ethylene)-(propylene-ethylene-1-butene) copolymer, and (propylene-1-butene)-(propylene -1-butene) copolymer, more preferably (propylene)-(propylene-ethylene) copolymer.

The polymer component (I) has an intrinsic viscosity ([η]I) of 0.1-5 dl/g, preferably 0.3-4 dl/g, more preferably 0.5-3dl/g.

The polymer component (II) has an intrinsic viscosity ([η]II) of 1-20 dl/g, preferably 1-10 dl/g, more preferably It is 2-7dl/g.

The ratio of the intrinsic viscosity ([η]II) of the polymer component (II) to the intrinsic viscosity ([η]I) of the polymer component (I) is preferably 1-20, more preferably 2-10, still more Preferably 2-9.

The intrinsic viscosity [η] (unit: dl/g) value in the present invention is measured by the method described below at 135° C. using tetralin as a solvent.

The reduced viscosities at three concentrations of 0.1 g/dl, 0.2 g/dl and 0.5 g/dl were measured using an Ubbelohde viscometer. The intrinsic viscosity is found by the calculation method described in "kobunshi Yoeki (Polymer Solution), Kobunshi Jikkengaku (Polymer Experiment) Vol. 11" page 491 (1982, published by Kyoritsu Shuppan Co., Ltd.), that is, using the reduced viscosity The relative concentrations were plotted and extrapolated by extrapolating the concentrations to zero.

When the propylene polymer (A) is a polymer material obtained by preparing polymer component (I) and polymer component (II) by multistage polymerization, polymer component (I) or polymer component (II) ) is measured using the polymer powder extracted from the polymerization tank of the first stage, and the intrinsic viscosity of the remaining components is calculated from the previously measured intrinsic viscosity and the content of the corresponding components.

Moreover, when the propylene copolymer consisting of polymer component (I) and polymer component (II) is polymer component (I) obtained in an earlier stage of polymerization step and polymer component (II) In the case of the copolymer obtained in the later step, the determination of the content of polymer component (I) and polymer component (II) and intrinsic viscosity ([η] total, [η]I, [η]II) and The calculation method is as follows, wherein the intrinsic viscosity ([η] total) represents the intrinsic viscosity of the propylene polymer (A) as a whole.

From the intrinsic viscosity ([η]I) of the polymer component (I) obtained in the polymerization step of the previous stage, the final polymer obtained after the polymerization step of the latter stage (polymer component (I) and polymer group Point (II)) the intrinsic viscosity ([η] total) measured by the above method and the content of the polymer component (II) contained in the final polymer, the intrinsic viscosity of the polymer component (II) is calculated by the following formula [ η] II:

[η]II=([η] total-[η]I×XI)/XII

[η] total: Intrinsic viscosity (dl/g) of the final polymer obtained after the polymerization step of the later stage

[η]I: Intrinsic viscosity (dl/g) of the polymer powder extracted from the polymerization reactor after the polymerization step of the earlier stage

XI: weight ratio of polymer component (I) relative to the overall propylene polymer (A)

XII: weight ratio of polymer component (II) relative to the overall propylene polymer (A)

XI and XII are calculated from the mass balance in the polymerization.

The weight ratio (XII) of the polymer component (II) relative to the overall propylene polymer (A) can be determined by determining the heat of crystal fusion of the propylene homopolymer component and the crystal fusion heat of the integral part of the propylene polymer (A), After that, it is determined by the following formula calculation. The heat of fusion of crystals can be determined by differential scanning calorimetry (DSC).

XII=1-(ΔHf)total/(ΔHf)

(ΔHf) total: heat of fusion (cal/g) of the entire portion of the propylene polymer (A)

(ΔHf): heat of fusion of propylene homopolymer component (cal/g)

The content of units derived from comonomers of the polymer component (II) in the propylene polymer (A) ((Cα')II) is measured by infrared absorption spectrometry from the integral fraction of the propylene polymer (A) The content of comonomer units ((Cα')total) is then calculated by the following formula and determined.

(Cα')II=(Cα')total/XII

(Cα') total: content (% by weight) of units derived from comonomers of the integral part of the propylene polymer (A)

(Cα')II: content (% by weight) of units derived from comonomers of the polymer component (II)

The block copolymer is obtained by preparing polymer component (I) in a first step and then preparing polymer component (II) in a second step. This polymerization is carried out using the above-mentioned polymerization catalyst.

<Ethylenically unsaturated bond-containing compound (B)>

The ethylenically unsaturated bond-containing compound (B) used in the present invention is a compound having at least one ethylenically unsaturated bond and at least one polar group. Examples thereof include unsaturated carboxylic acids and/or derivatives thereof such as unsaturated carboxylic acids, ester compounds of unsaturated carboxylic acids, amide compounds of unsaturated carboxylic acids, anhydrides of unsaturated carboxylic acids, unsaturated epoxy compounds, Unsaturated alcohols and unsaturated amine compounds.

More specific examples of the ethylenically unsaturated bond-containing compound (B) include:

(1) Maleic acid, maleic anhydride, fumaric acid, maleimide, maleic hydrazide, methyl norbornene diacid anhydride, dichloromaleic anhydride, maleamide, itaconic acid, itaconic acid Acid anhydride, glycidyl (meth)acrylate, 2-hydroxyethyl methacrylate, allyl glycidyl ether;

(2) Unsaturated carboxylic acids, such as acrylic acid, crotonic acid, crotonic acid, vinyl acetic acid, methacrylic acid, pentenoic acid, angelic acid, tiglic acid, 2-pentenoic acid, 3-pentenoic acid, alpha -Ethylacrylic acid, β-methylcrotonic acid, 4-pentenoic acid, 2-hexenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-2-pentenoic acid, α-ethyl Crotonic acid, 2,2-dimethyl-3-butenoic acid, 2-heptenoic acid, 2-octenoic acid, 4-decenoic acid, 9-undecenoic acid, 10-undecenoic acid , 4-dodecenoic acid, 5-dodecenoic acid, 4-tetradecenoic acid, 9-tetradecenoic acid, 9-hexadecenoic acid, 2-octadecenoic acid, 9 - octadecenoic acid, eicosenoic acid, docosenoic acid, erucic acid, tetracosenoic acid, mycolipidic acid, 2,4-hexadienoic acid, diallyl acetic acid, geranine acid, 2,4-Decadienoic acid, 2,4-Dodecadienoic acid, 9,12-Hexadecadienoic acid, 9,12-Octadecadienoic acid, Hexadecatrienoic acid, Di Decadedienoic acid, eicosatrienoic acid, eicosatetraenoic acid, ricinoleic acid, lyric acid, oleic acid, eicosapentaenoic acid, erucic acid, docosadienoic acid, eicosanoid Dicosatrienoic Acid, Docosatetraenoic Acid, Docosapentaenoic Acid, Tetracosenoic Acid, Hexadecenoic Acid, Hexadecadienoic Acid, Octacosaenoic Acid and tetradecenoic acid;

(3) ester compounds, amide compounds or acid anhydrides of unsaturated carboxylic acids as described above;

(4) Unsaturated alcohols, such as allyl alcohol, crotyl alcohol, methyl vinyl carbinol, allyl carbinol, methacryl carbinol, 4-penten-1-ol, 10-undecen-1- Alcohols, propargyl alcohol, 1,4-pentadien-3-ol, 1,4-hexadien-3-ol, 3,5-hexadien-2-ol, and 2,4-hexadiene -1-ol;

(5) Unsaturated alcohols, such as 3-butene-1,2-diol, 2,5-dimethyl-3-hexene-2,5-diol, 1,5-hexadiene-3, 4-diol, and 2,6-octadiene-4,5-diol; and

(6) An unsaturated amine obtained by substituting an amino group for a hydroxyl group of the above unsaturated alcohol.

Compounds (B) containing ethylenically unsaturated bonds are preferably unsaturated carboxylic acids and/or derivatives thereof, such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, (meth)acrylic acid Glycidyl esters, and 2-hydroxyethyl methacrylate, and maleic anhydride is particularly preferred.

Relative to 100 parts by weight of the propylene polymer (A), the amount of the ethylenically unsaturated bond-containing compound (B) added is 0.1-50 parts by weight, preferably 0.1-20 parts by weight, and more preferably 0.1-10 parts by weight parts, most preferably 0.1-5 parts by weight. If the added amount is less than 0.1 parts by weight, the graft ratio of the obtained modified propylene polymer may be low. If the added amount exceeds 50 parts by weight, it may have adverse effects on production, for example, the extruder may be corroded during the grafting reaction.

<Organic peroxide (C)>

The organic peroxide (C) used in the present invention is an organic peroxide that decomposes to generate radicals and then functions to remove protons on the propylene polymer (A). The organic peroxide (C) is preferably an organic peroxide whose decomposition temperature when the half-life becomes 1 minute is lower than 120°C, more preferably lower than 100°C, considering the proton removal behavior of the present invention at the heat treatment temperature.

In particular, the organic peroxide (C) is preferably at least one compound selected from the group consisting of a diacyl peroxide compound, a compound (b1) having a structure represented by the following structural formula (1), and A compound (b2) having a structure represented by the following structural formula (2)

[Chemical Structural Formula 1]

Examples of diacyl peroxide compounds include: dibenzoyl peroxide, diisobutyryl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, di(4-methylbenzoyl peroxide acyl) and dilauroyl peroxide.

Examples of the compound (b1) having a structure represented by the following structural formula (1) include: di(hexadecyl) peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di Di-2-ethylhexyl carbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, tert-butylperoxyisopropyl carbonate and di(deca Tetraalkyl) esters.

Examples of the compound (b2) having a structure represented by the following structural formula (2) include: 1,1,3,3-tetramethylbutyl neodecanoate, α-cumyl peroxyneodecanoate, peroxyneodecanoate tert-Butyl Oxyneodecanoate.

The organic peroxide (C) is added in an amount of 0.01-20 parts by weight, preferably 0.01-10 parts by weight, and still more preferably 0.1-5 parts by weight, relative to 100 parts by weight of the propylene polymer (A). If the added amount is less than 0.01 parts by weight, the graft ratio of the obtained modified propylene polymer may be low. If it exceeds 20 parts by weight, there may be an adverse effect on productivity, for example, the extruder may be corroded during the grafting reaction.

[Method for preparing modified propylene polymer]

The method for producing a modified propylene polymer according to the present invention has: a mixing step of mixing the propylene polymer (A), the ethylenically unsaturated bond-containing compound (B) and the organic peroxide (C); and, by using extrusion A heat treatment step in which the mixture obtained in the mixing step is heat-treated by a machine at a specified temperature. Each step will be described below.

<mixing step>

The mixing step is to mix 100 parts by weight of the propylene polymer (A) described below, 0.1 to 50 parts by weight of the ethylenically unsaturated bond-containing compound (B) based on the 100 parts by weight, and based on the 100 parts by weight Parts are 0.01-20 parts by weight of the organic peroxide (C) to carry out the step of mixing. It is preferable to uniformly mix the individual components by using a device such as a Henschel mixer and mixer. The mixing of the components is preferably performed at a temperature lower than the decomposition temperature at which the half-life of the organic peroxide (C) becomes 1 minute, preferably 1 second to 1 hour, more preferably 1 to 5 minutes.

<Heat treatment step>

The heat treatment step is a step of heat-treating the mixture obtained in the above mixing step at a predetermined temperature using an extruder. By heat treatment using an extruder, the organic peroxide (C) in the mixture is decomposed, the free radicals formed by the decomposition react with the propylene polymer (A), and the free radicals generated in the propylene polymer (A) react with the propylene polymer (A) containing The compound (B) having an ethylenically unsaturated bond reacts to become a modified propylene polymer capable of obtaining an increased melt tension.

The heat treatment temperature is preferably lower than the decomposition temperature at which the half-life of the organic peroxide (C) becomes 1 minute, more preferably from the glass transition temperature of the propylene polymer (A) to when the half-life of the organic peroxide (C) becomes The decomposition temperature at 1 minute is still more preferably from the glass transition temperature of the propylene polymer (A) to 100°C, still more preferably 20-80°C. If the heat treatment temperature exceeds the decomposition temperature at which the half-life of the organic peroxide (C) becomes 1 minute, the propylene polymer (A) will decompose so that the melt flow rate of the resulting modified propylene polymer will become high. By adjusting the heat treatment temperature to 20°C or higher, the load applied to the extruder can be reduced. The heat treatment temperature used in the present invention refers to the temperature of the cylinder of the extruder (the temperature of the kneading section).

The heat treatment time (residence time of the resin in the extruder) is 0.1-30 minutes, preferably 0.5-10 minutes.

Examples of extruders that can be used as the extruder used in the heat treatment step include: single-screw extruder, twin-screw extruder, multi-screw extruder, etc., and also, kneader, Banbury mixer machine, Brabender plasticizer, etc. In addition, extruders having a solid-phase shear zone, such as those disclosed in US4607797 and US6494390, and extruders having a melt-kneading zone in addition to a solid-phase shear zone, such as those disclosed in JP2005 - The extruder disclosed in 281379A.

In addition, a high-shear kneader equipped with an internal feedback screw can be used (see JP2005-313608A ). In particular, it is preferable to use an extruder capable of continuous production.

Two or more types of extruders selected from the above may be used together. For example, it allows the use of two types of extruders arranged in sequence (tandem, etc.) to separate the kneading step and the extrusion step. Extruders with two or more feed ports for raw materials can be used.

The extruder preferably has a raw material feeding section, a kneading section, a venting section, and an extrusion section. From the standpoint of productivity, the barrel temperature of the exhaust section and the extrusion section is preferably 100-300°C, more preferably 140-250°C. From the standpoint of eliminating heat generated by shearing, it is preferable that the screw and barrel be cooled with a coolant such as water.

Examples of the shape of the modified propylene polymer include: strands, sheets, flats, and pellets produced by cutting strand-like products. For molding the modified propylene polymer of the present invention, it is preferable that the polymer is in the form of pellets with a length of 1 to 50 mm from the viewpoint of production stability of the resulting molded article.

<additive>

Additives may be used in the modified propylene polymers of the present invention. Examples of additives include: neutralizers, antioxidants, UV absorbers, lubricants, antistatic agents, antiblocking agents, processing aids, colorants, foaming agents, foam nucleating agents, plasticizers, flame retardants agent, crosslinking agent, crosslinking aid, brightener, antibacterial agent, light diffusing agent. These additives may be used alone or in combination of two or more.

The resin composition according to the present invention may contain a resin or rubber component other than the propylene polymer (A) as described above.

Examples include ABS (copolymerized acrylonitrile/butadiene/styrene) resin, AAS (copolymerized specialty acrylic rubber/acrylonitrile/styrene) resin, ACS (copolymerized acrylonitrile/chlorinated polyethylene/styrene) Resin, polychloroprene, chlorinated rubber, polyvinyl chloride, polyvinylidene chloride, fluororesin, polyacetal, polysulfone, polyetheretherketone and polyethersulfone.

The modified propylene polymer according to the present invention can be blow molded, sheet formed, laminated and expanded.

[Example]

The present invention will be further described below with reference to examples and comparative examples. The propylene polymer (A), ethylenically unsaturated bond-containing compound (B) and organic peroxide (C) used in Examples and Comparative Examples are shown below.

· Propylene polymer (A)

(A-1) Propylene homopolymer

Melt flow rate (under 230°C and a load of 2.16Kgf): 18g/10min

Intrinsic viscosity ([η]): 1.34dl/g

(A-2) Propylene homopolymer

Melt flow rate (under 230°C and a load of 2.16Kgf): 105g/10min

Intrinsic viscosity ([η]): 0.93dl/g

・Ethylenically unsaturated bond-containing compound (B)

Compound name: maleic anhydride (MAH)

·Organic peroxide (C)

Compound name: Di(hexadecyl) peroxydicarbonate

Decomposition temperature when the half-life becomes 1 minute: 99°C

The physical properties of the raw material components and the modified propylene polymer were determined according to the methods given below.

(1) Melt flow rate (MFR; unit: g/10 minutes)

The melt flow rate of the raw material components and the modified propylene polymer was measured according to the method provided by JIS K7210. The measurement was performed at a temperature of 230° C. and a load of 2.16 Kg.

(2) Intrinsic viscosity ([η], unit dl/g)

The intrinsic viscosity of the raw material components was measured according to the following procedure. First, the reduced viscosity at three concentrations of 0.1, 0.2, and 0.5 g/dl was measured with an Ubbelohde viscometer. The intrinsic viscosity is then obtained by extrapolation, ie, by plotting the reduced viscosities against these concentrations separately, as previously described, and extrapolating the concentrations to zero. The measurements are carried out at 135° C. in tetralin.

(3) Modification rate using maleic anhydride (% by weight)

In each of Examples and Comparative Examples, a modified propylene polymer (1.0 g) was dissolved in 100 ml of xylene. The solution was added dropwise to 1000 ml of methanol under stirring, and then the reprecipitated modified propylene polymer was collected. The modified propylene polymer was dried under vacuum (80°C for 8 hours), and then a film with a thickness of about 100 μm was obtained by hot pressing. The infrared absorption spectrum of the thus-produced film was measured, and the absorbance of the characteristic absorption of the resulting infrared absorption spectrum was corrected using the thickness of the film sheet used for the measurement. Then, the modification ratio using maleic anhydride was measured by a calibration curve method based on the corrected absorbance. The peak at ¹⁷⁸⁰ cm was used as the characteristic absorption of maleic anhydride.

(4) Melt tension (MT, unit: cN)

As for the melt tension of the modified propylene polymer, the modified propylene polymer was passed through a hole having a diameter of 2.095 mm and a length of 8 mm at a temperature of 190° C. using a melt tension analyzer manufactured by Toyo Seiki Seisaku-sho, Ltd. Melt extrusion, the extrusion rate is 5.7 mm/min, the extruded modified propylene polymer is drawn into a thread by a drawing roller at a drawing speed of 15.7 m/min, and then the tension applied during the drawing process is measured. The average value of the maximum and minimum tensions measured during drawing was used as the melt tension.

[Example 1, Comparative Example 1]

Mix the propylene polymer (A), the ethylenically unsaturated bond-containing compound (B) and the organic peroxide (C) uniformly, and then use an extruder to perform heat treatment under the conditions given in Table 1 to obtain modified propylene polymer. A single-screw extruder was used as the extruder. The preset barrel temperature is 80° C., and the preset screw speed is 75 rpm. The blending ratio of the propylene polymer (A), the ethylenically unsaturated bond-containing compound (B) and the organic peroxide (C) and the physical properties of the resulting modified propylene polymer (A) are given in Table 1. out.

[Example 2-5, Comparative Example 2]

A modified propylene polymer was obtained in the same manner as in Example 1, except that the preset temperature of the barrel was set to 40° C. and the screw speed was set to 65 rpm in the corresponding Example. The physical properties of the obtained modified propylene polymer are shown in Table 1.

[Comparative example 3-6]

A modified propylene polymer was obtained in the same manner as in Example 1 except that a twin-screw extruder (Type TEX44αII-49BW-3V, manufactured by TheJapan SteelWorks, Ltd.) was used as the extruder. The barrel temperature of the extruder was adjusted to 200° C., and the screw speed was adjusted to 200 rpm.

[Table 1]

Comparative example 1 100 2 80 19.9 0.01 0.4 Comparative example 2 100 2 40 20.7 0.02 0.4 Comparative example 3 100 200 17.8 0.00 0.4 Comparative example 4 100 2 1 200 563 0.30 not measurable Comparative Example 5 100 2 1 200 360 0.10 not measurable Comparative example 6 100 2 2 200 349 0.19 not measurable

Claims (2)

1. a modified propylene polymer, described modified propylene polymer can by by the acrylic polymers of 100 weight portions (A),Based on described 100 weight portions be 0.1-50 weight portion containing the compound (B) of ethylenic unsaturated bond and based on described 100 weightOrganic peroxide (C) reaction that part is 0.01-20 weight portion obtains, the wherein said compound containing ethylenic unsaturated bond(B) be to select free maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, (methyl) glycidyl acrylate and firstAt least one member in the group of base acrylic acid 2-hydroxy methacrylate composition,

Wherein, under the load of 2.16Kg, meet 230 DEG C of melt flow rate (MFR)s that record with at 190 DEG C of melt tensions that recordFormula (1) below:

MT＞9×MFR^(－0.9)……(1)

Wherein MT is melt tension, and MFR is melt flow rate (MFR), and

Wherein modified propylene polymer under the load of 2.16Kg 230 DEG C of melt flow rate (MFR)s that record be 21.5 to200g/10 minute.

2. modified propylene polymer according to claim 1, the half-life of wherein said organic peroxide becomes 1 minuteTime decomposition temperature lower than 120 DEG C.